CN114835085A - Combined treatment method for titanium dioxide byproduct hydrochloric acid and chloride dust-collecting slag by chlorination process - Google Patents
Combined treatment method for titanium dioxide byproduct hydrochloric acid and chloride dust-collecting slag by chlorination process Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
- C01B7/0718—Purification ; Separation of hydrogen chloride by adsorption
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/125—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a sulfur ion as active agent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention discloses a combined treatment method of by-product hydrochloric acid and chlorinated dust-collecting slag of titanium dioxide by a chlorination method, which comprises the following steps: s1, adsorbing the byproduct hydrochloric acid by using resin, and removing colloid in the byproduct hydrochloric acid; s2, preparing the purified hydrochloric acid into a dilute acid solution with the hydrochloric acid mass concentration of 2-4%; s3, mixing the chlorinated dust-collecting slag with a dilute acid solution for pulping; s4, separating solid from liquid to collect dust and slag slurry; and using the primary filter residue as a titanium raw material for smelting the high-titanium slag. The advantages are that: 1) the method has the advantages that the titanium dioxide byproduct hydrochloric acid and the chloride dust-collecting slag are jointly treated for the first time, the titanium chloride slag is slurried after the dilute acid is prepared from the purified acid generated by adsorbing the byproduct hydrochloric acid by resin, and the technical problem that the chloride dust-collecting slag is difficult to filter due to a large amount of colloid generated by hydrolysis during slurrying is solved. 2) The method obviously reduces the treatment cost of waste acid and waste residue in the production process of titanium dioxide by a chlorination method, reduces the amount of waste discharged by the process, and is easy for industrial popularization.
Description
Technical Field
The invention relates to a titanium dioxide production technology, in particular to a byproduct treatment technology in titanium dioxide production by a chlorination process.
Background
At present, titanium dioxide production technologies are divided into a chlorination method and a sulfuric acid method, wherein the production capacity of the chlorination method accounts for about 56% globally, the production capacity of Chinese titanium dioxide is mainly based on the sulfuric acid method, and the production capacity of the chlorination method accounts for about 6.5% of the total production capacity of the domestic titanium dioxide. However, compared with the sulfuric acid method, the chlorination method has the advantages of short flow, good product quality, less three-waste emission and the like, so the production technology of titanium dioxide by the chlorination method is the national development technology process at present. But the production technology of titanium dioxide by chlorination method in China is always kept secret. The integrity and the technical advancement of the domestic chlorination process are far from foreign countries. In the production process of titanium dioxide by a chlorination process, a large amount of chemical agents including hydrochloric acid, sodium hypochlorite and the like are required to be used for separating, purifying and purifying intermediate products, so that waste residues and waste liquid are generated in the process.
In the waste gas treatment process, the waste gas is cleaned by a wet method, namely HCl and TiCl in the tail gas are washed by spraying water 4 Gas and byproduct 18-30% hydrochloric acid, because the tail gas is formedComplicated separation, high content of generated hydrochloric acid impurities, mainly containing silica gel and TiOCl 2 And dust and the like.
After condensation, the chlorination tail gas contains TiCl 4 、SiCl 4 And acidic gases such as HCl due to TiCl 4 、SiCl 4 Easy hydrolysis to respectively generate TiOCl 2 、H 4 SiO 4 Sol and hydrochloric acid, the reaction equation is as follows:
TiCl 4 +H 2 O＝TiOCl 2 +2HCl
SiCl 4 +4H 2 O＝H 4 SiO 4 +4HCl
the by-product hydrochloric acid contains a small amount of heavy metal ions in addition to high-concentration hydrochloric acid, and has a large amount of impurity components, a turbid appearance, and milky floccules, which makes it difficult to carry out an external selling treatment. At present, the main treatment mode is neutralization, a large amount of waste salt is generated after neutralization and cannot be utilized, the development of the chlorination method is limited, and the environmental risk is avoided. How to comprehensively utilize the part of waste hydrochloric acid, changing waste into valuable and comprehensively utilizing the waste hydrochloric acid is a future breakthrough point of the titanium dioxide production technology by the chlorination process.
Typical chemical compositions of a company's by-product hydrochloric acid are shown in the following table:
typical chemical composition of byproduct hydrochloric acid
| Sample name | TiO 2 ％ | HCl％ | Femg/L | SSmg/L | Simg/L |
| Byproduct hydrochloric acid 1# | 0.6 | 30.1 | 15.8 | 678 | 682.4 |
| Byproduct hydrochloric acid 2# | 0.6 | 28.1 | 29.5 | 760 | 49.63 |
| Byproduct hydrochloric acid 3# | 0.6 | 27.3 | 26.4 | 850 | 62.5 |
In the production of titanium dioxide by chlorination process, boiling chlorination process is adopted to prepare coarse TiCl 4 When in use, the high titanium slag raw material, chlorine and petroleum coke react with chlorine at high temperature to generate TiCl 4 、FeCl 2 、AlCl 3 And the metal chloride gas is mixed with a part of metal chloride of the petroleum coke and the high titanium slag fine particle materials which are not subjected to the reaction, the metal chloride is taken out by the airflow in the chlorination furnace and is captured by a cyclone dust collecting system to become byproduct chlorinated dust collecting slag, and the main components of the chlorinated dust collecting slag comprise ferrous chloride, ferric chloride, magnesium chloride, calcium chloride, a small amount of titanium tetrachloride and the like.
The chlorinated dust-collecting slag has complex components, can absorb water, hydrolyze, release heat and smoke due to metal chloride, titanium tetrachloride and the like in the transportation and stacking processes, generates a large amount of irritant gas, has great environmental and safety hazards, does not have a good treatment method in domestic and foreign enterprises at present, is treated by adopting a deep landfill or neutral stacking mode basically, can cause secondary pollution to water, soil and the like for a long time, and is also against the 'double reduction' policy advocated by the state. Aiming at the problem, a grading treatment process is innovatively provided by the company Limited Haifeng and Tai in Yibin Tianyuan at present, namely, the chlor-alkali and cement platform are combined to be recycled. In the process, after the chlorination slag is subjected to pulping, primary filter pressing and washing, neutralization, preconcentration, secondary filter pressing and washing procedures, primary filter residue (mainly comprising high titanium slag, petroleum coke and the like), secondary filter residue (mainly comprising metal hydroxide) and salt-containing wastewater are finally obtained, wherein the primary filter residue can be used for smelting titanium slag, the secondary filter residue is used for producing cement, and the salt-containing wastewater can be used for electrolyzing saturated salt water. The process has no secondary pollution and no waste discharge, realizes resource utilization of the chlorinated dust-collecting slag, and solves the problem that the chlorinated slag is difficult to treat.
However, in the production practice of the above process, it is found that more hydrolysis reactions occur during the pulping of chloride slag and a large amount of colloid flocs are generated, so that the subsequent filtration is extremely difficult, and the whole process flow is difficult to continue. Therefore, the process needs to be improved urgently, and the problem that the chlorinated slag slurry is difficult to filter is solved.
The composition of the first residue after drying in a certain company is shown in the following table:
primary residue major component (unit:%)
Chinese patent CN200610051995.X discloses a process for preparing high-purity hydrochloric acid by circularly absorbing hydrogen chloride byproducts, which comprises the steps of firstly, passing hydrogen chloride gas containing organic impurities through a condenser at-10 to-40 ℃ and a gas-liquid separator; then the gas containing a small amount of organic impurities from the gas-liquid separator is adsorbed by granular activated carbon; and introducing the adsorbed gas into a first-stage and a second-stage graphite falling film absorption towers, absorbing the gas by pure water to obtain the high-purity hydrochloric acid, absorbing unabsorbed hydrogen chloride by cold water, then feeding the unabsorbed hydrogen chloride and dilute acid in the graphite polypropylene falling film absorption tower into a cooling tank, and inputting the unabsorbed hydrogen chloride and the dilute acid into an inlet of the first-stage falling film absorption tower by a circulating pump for circulating absorption. The process has the advantages of large equipment investment, high energy consumption and low economic benefit.
Chinese patent CN202010944392.2 discloses a purification system and a purification process for hydrochloric acid as a byproduct of chlorination reaction, wherein the purification system comprises a negative pressure rectifying tower and a hydrogen chloride washing tower; the negative pressure rectification tower is characterized in that a first gas outlet is formed in the top of the negative pressure rectification tower, a byproduct hydrochloric acid inlet is formed in the upper portion of the negative pressure rectification tower, a first gas inlet is formed in the middle of the negative pressure rectification tower, a first circulating acid inlet is formed in the lower portion of the negative pressure rectification tower, a first circulating acid outlet is formed in the bottom of the negative pressure rectification tower, the first circulating acid outlet and the first circulating acid inlet are respectively connected with a circulating acid heater, a first purified acid outlet is formed in the lower portion of the negative pressure rectification tower, and the first purified acid outlet is connected with a first hydrochloric acid cooler. The method adopts the negative pressure rectifying tower to carry out negative pressure rectification on the byproduct hydrochloric acid, can effectively remove free chlorine and low-boiling-point organic matters in the byproduct hydrochloric acid, purify the acid to ensure that the content of the free chlorine or dichloromethane or alcohol and aldehyde is less than or equal to 50PPm, and can recover most hydrogen chloride gas.
Chinese patent CN202022031593.1 discloses a treatment system for waste hydrochloric acid and waste brine in titanium white chloride production. The utility model discloses a system carries out solitary preliminary treatment to waste hydrochloric acid and waste brine respectively, has got rid of pollutant wherein, carries out subsequent processing with both mixed regulations afterwards, has so not only realized the neutralization of the extremely strong waste water of acidity and basicity, has also avoided the secondary pollution that the chlorine that effective chlorine and sour direct contact produced brought. Besides, in the whole system of the utility model, except the generated sludge, no pollutant is discharged outside, and all the waste water and the crystallized salt can be reused for production.
Chinese patent CN201810541105.6 discloses a comprehensive treatment method for chlorination residue pulping wastewater, which comprises the following steps: 1) adding excessive sodium sulfate into calcium chloride wastewater generated by preparing titanium dioxide by a chlorination method, filtering after reaction,obtaining white gypsum and crude brine; 2) adding BaCl into crude brine 2 Adjusting SO in crude brine 4 2- The content is 3-5 g/L according to Ca in the crude brine 2+ 、Ba 2+ 、Sr 2+ Content, adding corresponding amount of BaCl 2 、Na 2 CO 3 Separating out precipitate after reaction to obtain finished salt water; 3) the finished brine is used as primary brine in chlor-alkali chemical industry.
Chinese patent CN201610362373.2 discloses a production process for preparing iron oxide red by using chlorination-process titanium dioxide byproduct chlorination slag, which adopts multi-stage purification measures to effectively purify the chlorination slag, extracts the ferrous chloride with main content in the chlorination slag to obtain high-purity ferrous chloride solution, simultaneously adopts a plurality of purification measures to improve the purity of the ferrous chloride solution, further prepares the ferrous chloride into pigment-grade iron oxide red, and adopts an effective coating process to improve the dispersibility and weather resistance of the iron oxide red.
Disclosure of Invention
In order to solve the problems that the hydrochloric acid byproduct of titanium dioxide and the chloridized dust-collecting slag are difficult to treat and the treatment cost is high in the prior chloridizing method, the invention provides a combined treatment method of the hydrochloric acid byproduct of titanium dioxide and the chloridized dust-collecting slag.
The technical scheme adopted by the invention is as follows: the combined treatment method of the chlorination-process titanium dioxide byproduct hydrochloric acid and the chlorination dust-collecting slag comprises the following steps:
s1, adsorbing the byproduct hydrochloric acid by using resin, and removing colloid to obtain purified hydrochloric acid;
s2, preparing the purified hydrochloric acid into a dilute acid solution with the hydrochloric acid mass concentration of 2-4%;
s3, mixing the chlorinated dust-collecting slag and the dilute acid solution for slurrying to obtain dust-collecting slag slurry;
s4, carrying out solid-liquid separation on the dust collection residue slurry to obtain primary filter residue and filtrate; because the main components of the primary slag are titanium dioxide and petroleum coke, the primary filter residue can be used as a titanium raw material for smelting high-titanium slag.
The invention utilizes the static adsorption principle, combines resin adsorption and conventional filtration to enrich colloid in the byproduct hydrochloric acid and effectively separate acid insoluble substances, thus creating conditions for the next chlorination dust-collecting slag treatment.
Experiments show that if industrial hydration slurry is adopted, the chlorination dust-collecting slag can be hydrolyzed to generate a large amount of colloid, so that the chlorination dust-collecting slag is difficult to filter, and the inventor finds that the purified hydrochloric acid obtained by resin adsorption in the previous step is diluted to 2-4% to carry out slurry conversion on the chlorination dust-collecting slag, so that the metal chloride can be inhibited from being hydrolyzed, and therefore, the combined utilization method is provided.
The invention improves the existing treatment process of the chlorination residue and the byproduct hydrochloric acid, and the byproduct hydrochloric acid after resin adsorption and filtration is used for chlorinating, collecting dust and slurrying, wherein the filter residue is recyclable primary filter residue. Experiments show that the primary filter residue can be used as a titanium-containing raw material produced by smelting high-titanium slag, and the quality of the primary filter residue completely meets the quality requirement of the titanium-containing material for electric furnace smelting. The filtrate can be used as hydrochloric acid solution for cyclic utilization, thereby improving the utilization rate of raw materials and reducing the discharge of three wastes. In addition, the resin used in the method can be recycled repeatedly, so that the resource utilization is maximized, and the method is an environment-friendly treatment method.
As a further improvement of the invention, the method also comprises the step of preparing secondary filter residue:
A. adjusting the pH of the filtrate by using a sodium hydroxide solution with the mass concentration of 30-35% until a large amount of precipitate is generated in the filtrate, so as to obtain secondary slurry;
B. and carrying out solid-liquid separation on the secondary slurry to obtain secondary filter residue, wherein the main components of the secondary filter residue are iron, aluminum and magnesium metal oxides and silicon dioxide, and are basically consistent with the components of the cement, so that the obtained secondary filter residue can be used as a raw material for producing the cement.
More preferably, a part of the filtrate may be returned to step S2 for preparing the dilute acid solution; and the rest filtrate is used for preparing the secondary filter residue.
As a further improvement of the invention, the resin is one or more selected from DM11 resin, LS1 resin and SD300 resin.
As a further improvement of the invention, the slurry is specifically as follows: weighing the chlorinated dust-collecting slag and the dilute acid according to the mass ratio of 1: 1-3, and uniformly stirring.
As a further improvement of the present invention, the adsorption is specifically: uniformly mixing the by-product hydrochloric acid with a resin content of 0.08-0.12 g per 100mL, and standing for more than 5min to obtain a mixed solution; and then, using a water circulation type vacuum pump to pump and filter the mixed solution under 0.08-0.10 MPa.
As a further improvement of the present invention, the solid-liquid separation specifically comprises: and carrying out suction filtration on the dust collection slag slurry by using a water circulation type vacuum pump under 0.08-0.10 MPa.
The invention also discloses a production method of the chlorination-process titanium dioxide, which is characterized by comprising a combined treatment method of the chlorination-process titanium dioxide byproduct hydrochloric acid and the chlorination dust-collecting slag.
The invention has the beneficial effects that: 1) the invention firstly proposes the combined treatment of the hydrochloric acid byproduct of titanium dioxide produced by the chlorination process and the chlorinated dust-collecting slag, prepares the diluted acid by using the purified acid produced by adsorbing the hydrochloric acid byproduct by resin, and then pulpifies the titanium chloride slag, solves the technical problem that the chlorinated dust-collecting slag is difficult to filter due to a large amount of colloid generated by hydrolysis during pulpifying, greatly improves the filtering performance of the chlorinated slag slurry, realizes the efficient recovery of petroleum coke and titanium in the chlorinated dust-collecting slag, effectively utilizes valuable substances in the chlorinated dust-collecting slag, and provides conditions for the subsequent preparation of secondary filter residue. 2) The method of the invention obviously reduces the treatment cost of waste acid and waste residue in the production process of titanium dioxide by a chlorination method, reduces the amount of waste discharged by the process, and reduces the cost of environmental protection treatment. The invention does not relate to new equipment and new materials, has small risk, higher economic and environmental protection benefits and is easy for industrialized popularization.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
The first embodiment is as follows:
the method comprises the following steps of jointly treating hydrochloric acid as a byproduct of titanium dioxide produced by a chlorination process and chlorination dust-collecting slag:
(1) 250ml of by-product hydrochloric acid (30%) is measured and added into a 500ml beaker, 0.25g of LS1 resin is added into the beaker, the mixture is stirred for 5min at the frequency of 30r/min, then the stirring is stopped, the mixture is kept stand for 10min, and the solution is filtered by a water circulation type vacuum pump at the pressure of 0.09MPa to obtain purified hydrochloric acid with the concentration of about 30%.
(2) Then the purified hydrochloric acid is prepared into dilute acid solution with the concentration of 3 percent.
(3) Weighing 150g of chlorinated dust-collecting slag and 150g of the dilute acid solution, adding into a 500ml beaker, and stirring for 10min at the frequency of 50r/min to obtain dust-collecting slag slurry.
(4) And (3) completing the suction filtration of the dust collection slag slurry by using a water circulation type vacuum pump for about 17min under 0.09MPa to obtain primary filter residue and filtrate, wherein the end point of the suction filtration is that the water content of the primary filter residue is 20%. And drying the primary filter residue for 2 hours at 120 ℃ to obtain the dried primary filter residue. Returning part of the filtrate to the step (2) for preparing the dilute acid solution, and using the rest of the filtrate for preparing secondary filter residue in the next step.
(5) And (3) fully reacting the residual filtrate with sufficient 32% sodium hydroxide solution to generate a yellow brown precipitate to obtain secondary slurry. And (3) using a water circulation type vacuum pump to complete suction filtration of the reacted secondary slurry under 0.09MPa to obtain secondary filter residue. And drying the secondary filter residue for 2 hours at the temperature of 120 ℃ to obtain the dried secondary filter residue.
Sampling and detecting the dried primary filter residue, wherein the components of the dried primary filter residue are shown in the table 1.
Example two:
the method comprises the following steps of jointly treating hydrochloric acid as a byproduct of titanium dioxide produced by a chlorination process and chlorination dust-collecting slag:
(1) 250ml of by-product hydrochloric acid (30%) is measured and added into a 500ml beaker, 0.25g of DM11 resin is added into the beaker, the mixture is stirred for 5min at the frequency of 30r/min, then the stirring is stopped, the mixture is kept stand for 10min, and the solution is filtered by a water circulation type vacuum pump under the pressure of 0.09MPa to obtain purified hydrochloric acid with the concentration of about 30%.
(2) Then the purified hydrochloric acid is prepared into dilute acid solution with the concentration of 3 percent.
(3) Weighing 100g of chlorinated dust-collecting slag and 200g of the dilute acid solution, adding into a 500ml beaker, and stirring for 10min at the frequency of 50r/min to obtain dust-collecting slag slurry.
(4) And (3) completing the suction filtration of the dust collection residue slurry by using a water circulation type vacuum pump for about 7min under 0.09MPa to obtain primary filter residue and filtrate, and drying the primary filter residue for 2h at 120 ℃ to obtain dried primary filter residue. Returning part of the filtrate to the step (2) for preparing the dilute acid solution, and using the rest of the filtrate for preparing secondary filter residue in the next step.
(5) And (3) fully reacting the residual filtrate with sufficient 32% sodium hydroxide solution to generate a yellow brown precipitate to obtain secondary slurry. And (3) using a water circulation type vacuum pump to complete suction filtration of the reacted secondary slurry under 0.09MPa to obtain secondary filter residue. And drying the secondary filter residue for 2 hours at the temperature of 120 ℃ to obtain the dried secondary filter residue.
Sampling and detecting the dried primary filter residue, wherein the components of the filter residue are shown in the table 1.
Example three:
the method comprises the following steps of jointly treating hydrochloric acid as a byproduct of titanium dioxide produced by a chlorination process and chlorination dust-collecting slag:
(1) 250ml of by-product hydrochloric acid (30%) is measured and added into a 500ml beaker, 0.25gSD300 resin is added into the beaker, the mixture is stirred for 5min at the frequency of 30r/min, then the stirring is stopped, the mixture is kept stand for 10min, and the solution is filtered by a water circulation type vacuum pump under the pressure of 0.09MPa to obtain purified hydrochloric acid with the concentration of about 30%.
(2) Then the purified hydrochloric acid is prepared into dilute acid solution with the concentration of 3 percent.
(3) And weighing 75g of chlorinated dust-collecting slag and 225g of the dilute acid solution, adding into a 500ml beaker, and stirring for 10min at the frequency of 50r/min to obtain dust-collecting slag slurry.
(4) And (3) completing the suction filtration of the dust collection residue slurry by using a water circulation type vacuum pump for about 5min under 0.09MPa to obtain primary filter residue and filtrate, and drying the primary filter residue for 2h at 120 ℃ to obtain dried primary filter residue. Returning part of the filtrate to the step (2) for preparing the dilute acid solution, and using the rest of the filtrate for preparing secondary filter residue in the next step.
(5) And (3) fully reacting the residual filtrate with sufficient 32% sodium hydroxide solution to generate a yellow brown precipitate to obtain secondary slurry. And (3) using a water circulation type vacuum pump to complete suction filtration of the reacted secondary slurry under 0.09MPa to obtain secondary filter residue. And drying the secondary filter residue for 2 hours at the temperature of 120 ℃ to obtain the dried secondary filter residue.
Sampling and detecting the dried primary filter residue, wherein the components of the filter residue are shown in the table 1.
Comparative example one:
the comparative example is a control experiment of the first example, and is different from the first example in that the chlorination dust-collecting slag is slurried by using industrial water, and the steps are as follows:
(1) 150g of chlorinated dust-collecting slag and 150g of industrial water are weighed, added into a 500ml beaker and stirred for 10min at the frequency of 50r/min to obtain dust-collecting slag slurry.
(2) And (3) using a water circulation type vacuum pump, and completing the suction filtration of the dust collection residue slurry under 0.09MPa for about 65min to obtain primary filter residue, wherein the suction filtration end point is that the water content of the primary filter residue is 20%.
As can be seen from the comparison between the first embodiment and the first comparative example, after the diluted acid solution is replaced by the industrial water, the suction filtration time for one-time filter residue to reach the same water content is increased from 17min to 65min, which shows that the filtering performance of the chlorinated slag slurry is greatly improved, and the technical problem that the chlorinated dust-collecting slag is difficult to filter due to a large amount of colloid generated by hydrolysis during slurrying is solved.
TABLE 1 EXAMPLES measurement results of dried residue composition (unit:%)
| Water content | C | TiO 2 | Cl | Fe | |
| Example one | 3.6 | 47.2 | 44.5 | 1.4 | 0.21 |
| Example two | 4.2 | 48.5 | 45.8 | 2.2 | 0.35 |
| EXAMPLE III | 1.4 | 51.7 | 44.9 | 0.5 | 0.37 |
As can be seen from Table 1, the primary filter residue prepared by the method can completely meet various index requirements of the titanium-containing material for electric furnace smelting in the titanium dioxide production process by the chlorination method, and the method provided by the invention is proved to have feasibility.
Claims (8)
1. The combined treatment method of the chlorination-process titanium dioxide byproduct hydrochloric acid and the chlorination dust-collecting slag comprises the following steps:
s1, adsorbing the byproduct hydrochloric acid by using resin, and removing colloid to obtain purified hydrochloric acid;
s2, preparing the purified hydrochloric acid into a dilute acid solution with the hydrochloric acid mass concentration of 2-4%;
s3, mixing the chlorinated dust-collecting slag and the dilute acid solution for slurrying to obtain dust-collecting slag slurry;
s4, performing solid-liquid separation on the dust collection slag slurry to obtain primary filter residue and filtrate; and using the primary filter residue as a titanium raw material for smelting the high-titanium slag.
2. The combined treatment method of hydrochloric acid as a byproduct of titanium dioxide and chlorinated dust-collecting slag by a chlorination process according to claim 1, further comprising the step of preparing secondary filter residue:
A. adjusting the pH of the filtrate by using a sodium hydroxide solution with the mass concentration of 30-35% until the filtrate generates a precipitate to obtain secondary slurry;
B. and carrying out solid-liquid separation on the secondary slurry to obtain secondary filter residue, and taking the secondary filter residue as a raw material for cement production.
3. The combined treatment method of hydrochloric acid as a byproduct of titanium dioxide and chlorinated dust-collecting slag by a chlorination process according to claim 2, which is characterized in that: returning a portion of the filtrate to step S2 for formulating the dilute acid solution; and the rest filtrate is used for preparing the secondary filter residue.
4. The method for jointly treating hydrochloric acid as a byproduct of titanium dioxide produced by a chlorination process and chlorinated dust-collecting slag according to any one of claims 1 to 3, wherein the method comprises the following steps: the resin is selected from one or more of DM11 resin, LS1 resin and SD300 resin.
5. The method for jointly treating hydrochloric acid as a byproduct of titanium dioxide produced by a chlorination process and chlorinated dust-collecting slag according to any one of claims 1 to 3, wherein the method comprises the following steps: the slurry preparation method specifically comprises the following steps: weighing the chlorinated dust-collecting slag and the dilute acid according to the mass ratio of 1: 1-3, and uniformly stirring.
6. The method for jointly treating hydrochloric acid as a byproduct of titanium dioxide produced by a chlorination process and chlorinated dust-collecting slag according to any one of claims 1 to 3, wherein the method comprises the following steps: the adsorption is specifically as follows: uniformly mixing the by-product hydrochloric acid with a resin content of 0.08-0.12 g per 100mL, and standing for more than 5min to obtain a mixed solution; and then, using a water circulation type vacuum pump to pump and filter the mixed solution under 0.08-0.10 MPa.
7. The method for jointly treating hydrochloric acid as a byproduct of titanium dioxide produced by a chlorination process and chlorinated dust-collecting slag according to any one of claims 1 to 3, wherein the method comprises the following steps: the solid-liquid separation specifically comprises the following steps: and carrying out suction filtration on the dust collection slag slurry by using a water circulation type vacuum pump under 0.08-0.10 MPa.
8. The production method of titanium dioxide by a chlorination process is characterized by comprising the following steps: the method for jointly treating hydrochloric acid as a byproduct of titanium dioxide produced by a chlorination process and chlorinated dust-collecting slag according to any one of claims 1 to 7.
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